EP1225160A2 - Mousse de carbone, mousse de graphite et leurs procédés de fabrication - Google Patents

Mousse de carbone, mousse de graphite et leurs procédés de fabrication Download PDF

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Publication number
EP1225160A2
EP1225160A2 EP02250459A EP02250459A EP1225160A2 EP 1225160 A2 EP1225160 A2 EP 1225160A2 EP 02250459 A EP02250459 A EP 02250459A EP 02250459 A EP02250459 A EP 02250459A EP 1225160 A2 EP1225160 A2 EP 1225160A2
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Prior art keywords
carbon
foam
temperature
pitch
mesophase pitch
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EP02250459A
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German (de)
English (en)
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EP1225160A3 (fr
Inventor
Koichi c/o Mitsubishi Gas Chemical Cie Inc Kanno
Hirotaka c/o Mitsubishi Gas Chem.Cie Inc Tsuruya
Ryuji c/o Mitsubishi Gas Chem. Cie Inc. Fujiura
Takeshi c/oMitsubishi Gas Chem.Cie Inc Koshikawa
Fumitaka c/oMitsubishi Gas Chem.Cie Inc Watanabe
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority claimed from JP2001013987A external-priority patent/JP2002220217A/ja
Priority claimed from JP2002000251A external-priority patent/JP4517563B2/ja
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Publication of EP1225160A2 publication Critical patent/EP1225160A2/fr
Publication of EP1225160A3 publication Critical patent/EP1225160A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0022—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors

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  • the present invention relates to a carbonaceous or graphitic carbon material which is obtained from a mesophase pitch as a raw material and which is excellent in heat resistance and chemical stability and has a uniform open cell structure and production processes of theses.
  • foam materials such as a plastic foam, obtained from a resin as a raw material are widely applied to heat insulating materials, cushioning materials or the like.
  • foam materials it is thought to apply foam materials to fields requiring various properties not heretofore required such as heat resistance, thermal conductivity, chemical stability, electrical conductivity, strength, gas diffusivity, etc.
  • the above fields include a gas diffusion electrode of a fuel cell, a bipolar plate and the like.
  • a conventional foam made of a thermoplastic resin can not be used. Accordingly, the use of a thermosetting resin foam, a carbon foam obtained by carbonizing a thermosetting resin foam or a foam made or a ceramic is discussed.
  • thermosetting resin-based foams form a hard-to-graphitize carbon
  • the thermosetting resin-based foams are poor in oxidation resistance at high temperatures or corrosion resistance in a chemical reaction and are insufficient in thermal conductivity.
  • foams made of a ceramic are excellent in oxidation resistance but are very poor in thermal conductivity and electrical conductivity.
  • a novel foam material having excellent properties such as high chemical stability, heat resistance, oxidation resistance, etc.
  • a novel foam material having excellent properties such as high chemical stability, heat resistance, oxidation resistance, etc.
  • TANSO 1992 [155] 370-378 I. Mochida, Y. Korai, K. Shimizu, S-H. Yoon, R. Fujiura.
  • USP6033506 also discloses a process of producing carbon foam wherein a pitch is heat-treated under the application of a pressure of up to 1,000 psi (approximately 6.8 MPa) with an inert gas to produce a carbon foam.
  • a foam material can be produced by heat-treating a pitch such as a mesophase pitch under the pressurization of an inert gas.
  • a pitch designed as a raw material for a foam has been not yet provided. Therefore, it is difficult to control the physical properties of a foam. Further, nonuniform parts exist in large quantities in a generated foam during the production of a foam so that the problem is that the yield of a product decreases as a result.
  • a special reactor which can endure a high temperature and a high pressure is required. Therefore, it is difficult to produce a foam industrially economically. Accordingly, it is required to control the nature of a carbon foam such as a bulk density under a low-pressure condition.
  • a carbon foam which is obtained by heat-treating a mesophase pitch whose softening point is 300 °C or less according to an elevated flow tester, whose ratio (Daromatic/Daliphatic) of the absorption intensity of an aromatic C-H stretching vibration, measured with FT-IR, to the absorption intensity of an aliphatic C-H stretching vibration, measured with FT-IR, is 4.0 or less and whose optically anisotropic content is at least 80 %.
  • the mesophase pitch is a pitch obtained by polymerizing a fused polycyclic hydrocarbon or a substance containing a fused polycyclic hydrocarbon in the presence of hydrogen fluoride and boron trifluoride.
  • a carbon foam as recited above which is obtained by heat-treating the above mesophase pitch at a temperature of from 400 °C to 800 °C under the application of pressure of 0.1 MPa or more with an inert gas.
  • a carbon foam which is obtained by further heat-treating the carbon foam obtained by the above heat-treatment at a temperature of from 600 °C to less than 2,000 °C.
  • a carbon foam as recited above which has a bulk density of from 0.20g/cm 3 to 0.65g/cm 3 and has a density, measured using helium as a substitution medium, of from 1.3 g/cm 3 to 1.5 g/cm 3 .
  • a graphite foam which is obtained by heat-treating the carbon foam recited above at a temperature of 2,000 °C or higher.
  • a graphite foam as recited above, which has a bulk density of from 0.3 g/cm 3 to 1.0 g/cm 3 and has a density, measured using helium as a substitution medium, of 2.0 g/cm 3 or more.
  • a graphite foam as recited above, which has a porosity of from 50 % to 90 % and an open cell rate of from 90 % to 100 %.
  • a carbon foam which is obtained by heat-treating, at a temperature of from 400 °C to 800 °C under the application of pressure of from 0.1 MPa to 5 MPa, preferably from 0.1 MPa to 4 MPa, more preferably from 0.1 MPa to 3 MPa, with an inert gas, at least one mesophase pitch selected from the group consisting of the following mesophase pitches a, b, c and d which are obtained by polymerizing a fused polycyclic hydrocarbon or a substance containing a fused polycyclic hydrocarbon in the presence of hydrogen fluoride and boron trifluoride as catalysts,
  • a process for the production of a carbon foam comprising heat-treating at least one mesophase pitch selected from the group consisting of the above a, b, c and d at a temperature of from 400 °C to 800 °C under the application of pressure of from 0.1 MPa to 5 MPa, preferably from 0.1 MPa to 4 MPa, more preferably from 0.1 MPa to 3 MPa, with an inert gas.
  • a process for the production of a carbon foam comprising pulverizing at least one mesophase pitch selected from the group consisting of the above a, b, c and d, molding the pulverized mesophase pitch at a room temperature or under heat and then heat-treating the molded mesophase pitch at a temperature of from 400 °C to 800 °C under the application of pressure of from 0.1 MPa to 5 MPa, preferably from 0.1 MPa to 4 MPa, more preferably from 0.1 MPa to 3 MPa, with an inert gas.
  • a carbon foam which is obtained by further heat-treating the carbon foam obtained from at least one mesophase pitch selected from the group consisting of the above a, b, c and d at a temperature of from 600 °C to less than 2,000 °C. Owing to this treatment, a density, electrical physical properties and thermally physical properties can be controlled in proper ranges suited for an intended use.
  • a process for the production of a carbon foam which process comprises further heat-treating the above carbon foam at a temperature of from 600 °C to less than 2,000 °C.
  • a graphite foam having a bulk density of 0.30 g/cm 3 or more, which is obtained by heat-treating the above carbon foam at a temperature of 2,000 °C or higher.
  • a process for the production of a graphite foam which process comprises heat-treating the above carbon foam at a temperature of 2,000 °C or higher.
  • the present inventors have made diligent studies for overcoming the above problems and as a result found that a fine carbon foam can be obtained by heat-treating a specific mesophase pitch.
  • the heat-treatment is preferably carried out under the application of pressure of 0.1 MPa or higher with an inert gas and at a temperature of from 400 °C to 800 °C.
  • the present inventors have found that a specific carbon foam having a uniform open cell structure can be accordingly industrially stably produced. Further, the present inventors have found that a specific graphite foam having a uniform open cell structure can be stably produced by further heat-treating the above carbon foam at a temperature of 2,000 °C or higher. On the basis of these findings, the present inventors have reached the present invention 1.
  • a fine carbon foam can be produced by the use of a specific mesophase pitch, as a raw material, prepared from a pitch obtained by polymerizing a fused polycyclic hydrocarbon or a substance containing a fused polycyclic hydrocarbon in the presence of hydrogen fluoride and boron trifluoride as catalysts, even when the applied pressure with an inert gas when the carbon foam is produced by heat-treatment at a temperature of 400 °C or higher is 0.1 to 5 MPa, preferably 0.1 to 4 MPa, more preferably 0.1 to 3 MPa.
  • the present inventors have reached the present invention 2.
  • Some of the above carbon foam can satisfy the requirement that the bulk density is 0.20 g/cm 3 or more.
  • the present inventors have found that a graphite foam having a bulk density of 0.30 g/cm 3 or more can be stably produced by heat-treating the above carbon foam at a temperature of 2,000 °C or higher. On the basis of the finding, the present inventors have reached the present invention 2.
  • the raw material mesophase pitch used in the present invention 1 may be a mesophase pitch of petroleum type, coal type or synthetic type, it is a mesophase pitch whose softening point is 300 °C or less according to a flow tester method, whose ratio (Daromatic/Daliphatic) of the absorption intensity of an aromatic C-H stretching vibration, measured with FT-IR, to the absorption intensity of an aliphatic C-H stretching vibration, measured with FT-IR, is 4.0 or less and whose optically anisotropic content is at least 80 %.
  • the above specific pitch is heat-treated under the application of a pressure of preferably 0.1 MPa or more with an inert gas at a temperature of from 400 °C to 800 °C
  • the mechanism where the carbon foam having a uniform open cell structure is produced from the above specific pitch is not entirely obvious, the mechanism is estimated as follows.
  • the pitch is converted into a high viscosity pitch due to a condensation reaction at a high temperature of 400 °C or higher and finally the pitch is solidified.
  • a cracked gas generated in tandem with this works as a foaming agent to form a foam.
  • a practical foam having a bulk density of at least a certain level can be produced when the above reaction is carried out under the application of a pressure with an inert gas.
  • the pitch has a very high softening point of more than 300°C, the fluidity of the pitch during melting is poor in a foam-producing step to be described later. In this case, therefore, it is difficult to convert the pitch into a uniform block having no bubbles in a die before the formation of a foam so that voids which are a cause of a decrease in strength are apt to occur inside a foam as a product, which is not preferred industrially.
  • optically anisotropic content When the optically anisotropic content is less than 80 %, cells of a foam generated become nonuniform.
  • optically anisotropic content is less than 10 %, i.e., a substantially isotropic pitch is used, a fine foam can not be produced from any of the types of a petroleum type, a coal type and a synthetic type.
  • the ratio (Daromatic/Daliphatic) of the pitch which is a ratio of the absorption intensity of an aromatic C-H stretching vibration, measured with FT-IR, to the absorption intensity of an aliphatic C-H stretching vibration, measured with FT-IR, is more than 4.0 and the aromatic carbon index fa value of the pitch is more than 0.97
  • the retentional amount of aliphatic hydrogen effective as a foaming agent in the pitch is assumed to be small, so that a fine cell structure can not be obtained.
  • the pitch has an aromatic carbon index fa value of less than 0.80, industrially undesirably, a fine cell structure is not formed either and at the same time the carbonization yield is small.
  • a mesophase pitch whose softening point is in the range of from 180 °C to 270 °C according to a flow tester method, whose ratio (Daromatic/Daliphatic) of the absorption intensity of an aromatic C-H stretching vibration, measured with FT-IR, to the absorption intensity of an aliphatic C-H stretching vibration, measured with FT-IR, is in the range of from 0.4 to 2.0, whose aromatic carbon index fa value is in the range of from 0.83 to 0.93 and whose optically anisotropic content is 100 % in order to obtain the uniformity of cell structure of a carbon foam and at the same time to improve the productivity of a foam.
  • a synthetic mesophase pitch obtained by polymerizing a fused polycyclic hydrocarbon or a substance containing a fused polycyclic hydrocarbon in the presence of hydrogen fluoride and boron trifluoride is preferably used since it satisfies all the above conditions necessary to obtain a carbon foam having a fine cell structure and at the same time it has a high chemical purity, excellent graphitizing properties and a very high carbonization yield.
  • the mesophase pitch used in the present invention 2 is at least one mesophase pitch selected from the group consisting of the following mesophase pitches a, b, c and d which are obtained by polymerizing a fused polycyclic hydrocarbon or a substance containing a fused polycyclic hydrocarbon in the presence of hydrogen fluoride and boron trifluoride as catalysts,
  • the above mesophase pitch is suited for the production of a carbon foam having a bulk density of 0.20 g/cm 3 or more.
  • the method of the above a in which the heat-treatment is carried out after the polymerization to obtain a mesophase pitch, is carried out by polymerizing a fused polycyclic hydrocarbon under an authigenic pressure in the presence of catalysts, then reducing the pressure to recover the catalysts, and heat-treating the resultant pitch at a maximum treatment temperature of 300 °C or higher.
  • an inert gas such as nitrogen may be introduced similarly to a general light-contents-removing procedure.
  • a carbon foam having a bulk density of 0.20 g/cm 3 or more can be obtained by carrying out the heat-treatment under the application of a pressure of from 0.1 MPa to 5 MPa, preferably from 0.1 MPa to 4 MPa, more preferably from 0.1 MPa to 3 MPa, with an inert gas at a temperature of from 400 °C to 800 °C. It is estimated that a pitch having an aromatic carbon index fa of more than 0.97 has a small retentional amount of aliphatic hydrogen effective as a foaming agent, so that a fine cell structure can not be obtained.
  • a carbon foam having a bulk density of 0.20 g/cm 3 or more can not be produced from a pitch having an aromatic carbon index fa of less than 0.90 under the application of a pressure of 3 MPa or less with an inert gas.
  • an effective method is a method in which the molar ratio of boron trifluoride among the catalysts to naphthalene is decreased to 0.1 or less.
  • a catalyst molar ratio fused polycyclic hydrocarbon/hydrogen fluoride/boron trifluoride
  • a mesophase pitch having an aromatic carbon index fa value of from 0.90 to 0.97 can not be obtained under the above reaction conditions in some cases, a carbon foam having a bulk density of 0.20 g/cm 3 or more can be obtained under the application of pressure of 3 MPa with an inert gas.
  • a mesophase pitch having a fa value of from 0.90 to 0.97 which is effective for increasing the bulk density of a foam, can be produced so that such meltability that the softening point determined with a flow tester is 300 °C or less can be maintained. For this reason, it is preferred in view of the production of a carbon foam having an arbitrary form by the use of a die.
  • the solvent for extraction is selected from various solvents such as hexane, benzene, toluene, pyridine, quinoline and chloroform, a tar wash oil and the like.
  • the method of heat-treating the specific pitch described before under the application of pressure of from 0.1 MPa to 5 MPa, preferably from 0.1 MPa to 4 MPa, more preferably from 0.1 MPa to 3 MPa, with an inert gas at a temperature of from 400 °C to 800 °C, is not specially limited. According to the use of the mesophase pitch of the present invention, a carbon foam having a uniform open cell structure is relatively easily produced.
  • the physical properties of a foam such as a cell structure or a bulk density can be controlled not only by the pressure with an inert gas or the temperature-increasing rate but also by combining the selection of a pitch with these production conditions.
  • the method of placing a mesophase pitch into a pressure vessel includes a method (A) in which a mesophase pitch in a powder, pellet or block state is placed in a metal vessel such as a vessel made of aluminum or a vessel made of stainless steel for forming a foam, a method (B) in which a mesophase pitch is placed in a metal vessel made of aluminum or stainless steel, the metal vessel is placed in a heating furnace, and the mesophase pitch is maintained under a nonoxidative atmosphere of a nitrogen current at a temperature higher than the softening point by approximately 100 °C for approximately 10 hours to convert the mesophase pitch into a uniform block containing almost no bubbles in the metal vessel, and a method (C) in which a pitch is pulverized and then molded at room temperature or under heat and then the molded pitch is placed in a vessel made of aluminum, stainless steel or the like.
  • the method (C) in which a pitch is pulverized and then molded at room temperature or under heat and then the molded pitch is placed in a vessel is effective for obtaining a uniform carbon foam when the softening point of a raw material mesophase pitch which satisfies the parameter of the present invention is increased and therefore it is difficult to obtain a uniform block containing almost no bubbles in a metal vessel.
  • the method of heat-treating a mesophase pitch which is pressure-increased to 0.1 MPa or higher by means of an inert gas, at a temperature of from 400 °C to 800 °C is not specially limited, for example, the following methods may be adopted.
  • a metal vessel containing a mesophase pitch is placed in a heatable pressure vessel, the atmosphere is replaced with a nitrogen atmosphere by a vacuum substitution, then, the temperature is increased up to 350 °C at a rate of 3°C/minute while keeping atmospheric pressure and the mesophase pitch is maintained for 1 hour. Then, the pressure is increased to 3.0 MPa with nitrogen while keeping the temperature of 350 °C and the temperature is increased up to 550 °C at a rate of 2 °C/minute. The mesophase pitch is maintained for 1 hour in this state, then the heater is turned off, and the mesophase pitch in the metal vessel is allowed to cool naturally in the furnace.
  • the obtained carbon foam can be successively heat-treated at a temperature of from 600 °C to less than 2,000 °C.
  • the pressure in this heat treatment may be a normal pressure or a pressurized pressure. Owing to the above heat-treatment, a density, electrical physical properties and thermally physical properties can be controlled in proper ranges.
  • the above carbon foam is graphitized by heat-treating at a temperature of 2,000 or higher, whereby a graphite foam having a bulk density of 0.3 g/cm 3 or more is produced.
  • the above graphite foam can be a foam having high strength and high thermal conductivity.
  • the pitch specified by the present invention 1 is heat-treated under the application of a pressure of 0.1 MPa or more with an inert gas at a temperature of from 400 °C to 800 °C, whereby there is produced a carbon foam which has a bulk density d of from 0.20 g/cm 3 to 0.65 g/cm 3 , a density D, measured using helium as a substitution medium, of from 1.3 g/cm 3 to 1.5 g/cm 3 , a porosity p of from 50 % to 90 % and an open cell rate of from 90 % to 100 %, and of which the optical texture of the carbon is substantially 100 % anisotropic.
  • the carbon foam having the above specific values of physical properties has a uniform open cell structure, and there can be provided a novel carbon foam having uniform gas diffusivity into the foam or the like in addition to properties such as heat resistance, chemical stability, electrical conductivity and strength.
  • the above carbon foam is graphitized by heat-treating at a temperature of 2,000 or higher, whereby there is produced a graphite foam having a bulk density of from 0.3 g/cm 3 to 1.0 g/cm 3 , a density, measured using helium as a substitution medium, of from 2.0 g/cm 3 or more, a porosity of from 50 % to 90 % and an open cell rate of from 90 % to 100 %.
  • a heat-treated carbon foam obtained by heat-treating the carbon foam at a temperature of from 400 °C to 2,000 °C before the graphitization may be used as a raw material for producing a graphite foam.
  • the mesophase pitch specified by the present invention 2 is heat-treated under the application of from 0.1 MPa to 5 MPa, preferably from 0.1 MPa to 4 MPa, more preferably from 0.1 MPa to 3 MPa, with an inert gas at a temperature of from 400 °C to 800 °C, whereby a carbon foam having a bulk density of 0.20 g/cm 3 or more can be obtained. Further, the above carbon foam is furthermore heat-treated at a temperature of 2,000 °C or higher, whereby a graphite foam having a bulk density of 0.3 g/cm 3 or more can be produced.
  • the graphite foam having the above specific values of physical properties has high thermal conductivity in addition to a uniform open cell structure, heat resistance, chemical stability, electrical conductivity, strength and gas diffusivity which the carbon foam of the present invention has, since it is derived from an excellent easy-to-graphitize carbon.
  • a carbon foam having a uniform open cell structure As described in detail above, owing to the use of the raw material pitch based on the present invention 1, there can be industrially stably produced a carbon foam having a uniform open cell structure. Further, owing to the use of the raw material pitch based on the present invention 2, there can be produced a carbon foam having a uniform open cell structure at such a pressure of 5 MPa or less, preferably 4 MPa or less, more preferably 3 MPa or less, that an operation can be industrially stably performed. Further, a graphite foam having a uniform open cell structure together with a high graphitization degree can be industrially stably produced by graphitizing the above carbon foam at 2,000 °C or higher.
  • the softening point was measured with an elevated flow tester supplied by SHIMADZU CORPORATION.
  • a cylinder having a sectional area of 1 cm 2 and having a nozzle having a diameter of 1 mm at a bottom was charged with 2 g of a sample which had been pulverized to 300 microns or less and the temperature was increased at a rate of 5 °C/minute while applying a pressure of 9.8 N/cm 2 (10kg/cm 2 ).
  • Powder particles softened with increasing the temperature, to increase the filling rate and to decrease the volume of the sample powder. However, the volume decrease stopped when the temperature exceeded a certain temperature. When the temperature-increase was further continued, the sample melted and flowed out from the nozzle. In this case, the temperature at which the volume decrease of the sample powder stopped was defined as a softening point.
  • the density using helium as a substitution medium was measured with a micropycnometer supplied by Quantachrome. A sample was dried at 120 °C for 2 hours.
  • the softening point of the above pitch according to a flow tester was 227 °C.
  • the atom ratio (H/C) of hydrogen to carbon was 0.606.
  • the ratio (Daromatic/Daliphatic) of the absorption intensity of an aromatic C-H stretching vibration, measured with FT-IR, to the absorption intensity of an aliphatic C-H stretching vibration, measured with FT-IR, was 0.507.
  • the aromatic carbon index fa value calculated by the formula (1) was 0.85.
  • the optically anisotropic content of the pitch according to an observation with a polarization microscopy was 100 %, and the pitch was a mesophase pitch.
  • the aluminum vessel containing the pitch was placed in an airtight container made of SUS and having an outer diameter of 25 mm, an internal diameter of 20 mm and a length of 160 mm.
  • the airtight container made of SUS was set in the center of a crucible furnace equipped with a thermoregulator and having an internal diameter of 105 mm.
  • the atmosphere in the airtight container was changed to a nitrogen atmosphere by a vacuum substitution.
  • the temperature was increased up to 350 °C at a rate of 3°C/minute with retaining atmospheric pressure, and the mesophase pitch was maintained for 1 hour in this state.
  • the pressure was increased to 6.5 MPa with nitrogen while keeping the temperature of 350 °C and then the temperature was increased up to 550 °C at a rate of 2 °C/minute.
  • the pressure at 550 °C was 8.6 MPa.
  • the mesophase pitch was maintained for 1 hour in this state, then the heater was turned off, and the airtight container made of SUS was allowed to cool naturally in the furnace. Thereafter, a sample was taken out and it was found that the pitch was foamed and carbonized in the aluminum vessel to form a carbon foam.
  • the carbon foam in the aluminum vessel was estimated for bulk density
  • the carbon foam was cut with a diamond cutter to obtain a sample, and the sample was measured for a density using helium.
  • the bulk density was 0.43 g/cm 3
  • the density measured using helium as a substitution medium was 1.40 g/cm 3 .
  • a carbon foam separately prepared in the same manner as above was pulverized to 150 microns or less and then measured for a density Dr using helium as a substitution medium.
  • the density Dr was 1.44 g/cm 3 . Therefore, the porosity was calculated to find that it was 70 %. And the open cell rate was calculated to find that it was 97 %.
  • the carbon foam was observed through a polarization microscope by a conventional method to find that the optical texture of the carbon constituting the foam was 100 % anisotropic. Further, the cross section of the foam was observed with SEM and it was found that the carbon foam was a fine carbon foam having a very uniform cell shape as shown in Fig. 1.
  • the carbon foam was temperature-increased under a nitrogen atmosphere at a rate of 10 °C/hour. After the temperature reached to 1,000°C, the temperature was maintained for 2 hours to calcinate the carbon foam. Successively, the carbon foam was temperature-increased under an argon atmosphere at a rate of 500 °C/hour. At 2,800 °C, a graphitization treatment was carried out for 1 hour, to form a graphite foam.
  • the graphite foam had a bulk density of 0.55 g/cm 3 , and the density measured using helium as a substitution medium was 2.185 g/cm 3 .
  • a graphite foam separately prepared in the same manner as above was pulverized to 150 microns or less and then measured for a density Dr using helium as a substitution medium.
  • the density Dr was 2.230 g/cm 3 . Therefore, the porosity was calculated to find that the graphite foam had a porosity of 75 %. And the open cell rate was calculated to find that the graphite foam had an open cell rate of 98 %.
  • the crystal structure of the graphite foam powder was analyzed by an X-ray diffraction method (method of the Japan Society for Promotion of Scientific Research) .
  • the spacing d002 of crystallite on the surface (002) was 0.3359 nm
  • the size Lc of crystallite was 120 nm
  • the graphite foam had a high graphitization degree. Table 1 shows the results.
  • Example 1 The same raw material pitch as that in Example 1 was used, and an investigation was carried out in the same manner as in Example 1 except that the pressure was increased to 3.5 MPa with nitrogen while keeping the temperature of 350 °C and the temperature was increased up to 550 °C at a rate of 2 °C/minute. Tables 1 and 2 show the results.
  • Example 2 10 g of the same pitch as that synthesized in Example 1 was placed in a 100-cc beaker, the 100-cc beaker was placed in a muffle furnace in which a nonoxidative atmosphere was kept, the temperature was increased up to 425 °C at a rate of 250 °C/hour, and then the pitch was maintained for 1 hour in this state. After cooling to 100 °C or lower, the pitch in the beaker was taken out. The yield was 95.5 %. The thus-obtained pitch was used as a raw material, and a foam production and an investigation were carried out in the same manner as in Example 1. Table 2 shows the results.
  • Example 2 An investigation was carried out in the same manner as in Example 1 except that the raw material pitch was replaced with a petroleum type mesophase pitch. Table 2 shows the results.
  • Example 2 An investigation was carried out in the same manner as in Example 2 except that the raw material pitch was replaced with a coal type mesophase pitch. Table 2 shows the results.
  • Example 2 An investigation was carried out in the same manner as in Example 2 except that the raw material pitch was replaced with a coal type mesophase pitch. Table 2 shows the results.
  • a raw material pitch (coal-tar type mesophase pitch) had the following properties.
  • the softening point according to a flow tester was 176 °C.
  • the atom ratio (H/C) of hydrogen to carbon was 0.424.
  • the aromatic carbon index fa value calculated by the formula (1) was 0.983.
  • the optically anisotropic content according to an observation with a polarization microscopy was 80 %.
  • a carbon foam was produced from the above mesophase pitch as a raw material in the same manner as in Example 1.
  • the bulk density was 0.50 g/cm 3 and the density measured using helium as a substitution medium was 1.32 g/cm 3 .
  • a carbon foam separately prepared in the same manner as above was pulverized to 150 microns or less and then measured for a density Dr using helium as a substitution medium.
  • the density Dr was 1.48 g/cm 3 . Therefore, the porosity was 66 %.
  • the carbon foam had a low open cell rate of 89 %.
  • the carbon foam was observed through a polarization microscope by a conventional method to find that the optical texture of the carbon constituting the foam was 100 % anisotropic.
  • the cross section of the foam was observed with SEM and it was found that the carbon foam had nonuniform cells as shown in Fig. 3. Table 3 shows the results.
  • the softening point of the above pitch according to a flow tester was 93 °C.
  • the atom ratio (H/C) of hydrogen to carbon was 0.75.
  • the ratio (Daromatic/Daliphatic) of the absorption intensity of an aromatic C-H stretching vibration, measured with FT-IR, to the absorption intensity of an aliphatic C-H stretching vibration, measured with FT-IR, was 0.256.
  • the aromatic carbon index fa value calculated by the formula (1) was 0.752.
  • the optically anisotropic content of the pitch according to an observation with a polarization microscopy was 0 %, and the pitch was an isotropic pitch.
  • a carbon foam was produced from the above mesophase pitch as a raw material in the same manner as in Example 1.
  • the bulk density was 0.48 g/cm 3 and the density measured using helium as a substitution medium was 1.33 g/cm 3 .
  • a carbon foam separately prepared in the same manner as above was pulverized to 150 microns or less and then measured for a density Dr using helium as a substitution medium.
  • the density Dr was 1.43 g/cm 3 . Therefore, the porosity was 66 % and the open cell rate was 93 %.
  • the carbon foam was observed through a polarization microscope by a conventional method to find that the optical texture of the carbon constituting the foam was 100 % anisotropic. However, the cross section of the foam was observed with SEM, to find that the carbon foam had nonuniform cells as shown in Fig. 4. Table 3 shows the results.
  • Example 3 An investigation was carried out in the same manner as in Example 1 except that the raw material pitch was replaced with a petroleum type mesophase pitch. Table 3 shows the results.
  • Example 1 An investigation was carried out in the same manner as in Example 1 except that the raw material pitch was replaced with a coal-tar pitch. Table 3 shows the results.
  • Examples 1,2 3,4 5 Raw material naphthalene naphthalene naphthalene Synthetic temperature (°C) 265 245 285 Catalyst ratio in synthesis 1/0.35/0.15 1/0.32/0.074 1/0.7/0.20 Softening point(°C) 227 220 255 H/C 0.606 0.590 0.593 Daroma/Dalipha 0.507 0.576 0.516 fa 0.850 0.863 0.854 anisotropic content (%) 100 100 100 Carbon foam Examples 1 2 3 4 5 Pressure(350°C, MPa) 6.5 3.5 6.5 3.5 6.5 Bulk density d (g/cm 3 ) 0.43 0.27 0.47 0.32 0.49 He density D (g/cm 3 ) 1.40 1.41 1.38 1.36 1.38 True density Dr (g/cm 3 ) 1.44 1.
  • HF-BF 3 superacid catalyst HF-BF 3
  • the above mesophase pitch was further heat-treated at 470°C for 0.5 hour to obtain a heat-treated mesophase pitch having a softening point of 295 °C according to a flow tester, a (H/C) of 0.526, a (Daromatic/Daliphatic) of 1.34 and an aromatic carbon index fa value of 0.929.
  • the temperature was increased up to 350 °C at a rate of 3°C/minute with retaining atmospheric pressure, and the heat-treated mesophase pitch was maintained for 1 hour in this state.
  • the pressure was increased to 3.0 MPa, and then the temperature was increased up to 550 °C at a rate of 2 °C/minute while keeping the pressure of 3 MPa.
  • the heat-treated mesophase pitch was maintained for 1 hour in this state.
  • the heater was turned off, and the airtight container made of SUS was allowed to cool naturally in the furnace. Thereafter, a sample was taken out and it was found that the pitch was foamed and carbonized in the aluminum vessel to form a carbon foam.
  • the carbon foam in the aluminum vessel had a bulk density of 0.36 g/cm 3 .
  • the carbon foam was temperature-increased under a nitrogen atmosphere at a rate of 10 °C/hour. After the temperature reached to 1,000 °C, the tempearture was maintained for 2 hours to calcinate the carbon foam. Successively, the carbon foam was temperature-increased under an argon atmosphere at a rate of 500 °C/hour. At 2,800 °C, a graphitization treatment was carried out for 1 hour, to form a graphite foam. The graphite foam had a bulk density of 0.47 g/cm 3 . Table 4 shows the results.
  • Example 11 The same mesophase pitch as that used in Example 11 was heat-treated at 475 °C for 0.5 hour, to obtain a heat-treated mesophase pitch having a softening point of 300 °C or higher according to a flow tester, a (H/C) of 0.492, a (Daromatic/Daliphatic) of 1.806 and an aromatic carbon index fa value of 0.947.
  • the heat-treated mesophase pitch was pulverized with a coffee mill, 8 g of the pulverized mesophase pitch was pressure-formed under 3 MPa to obtain a disk pitch molded material having a diameter of 28 mm and a thickness of 13 mm and having a bluk density of 1.1 g/cm 3 .
  • the pitch molded material was placed in a cylindrical vessel which was made of aluminum and had an internal diameter of 31 mm, a depth of 40 mm and an internal volume of 30.175 cm 3 , and the cylindrical vessel was placed in the same airtight container made of SUS as that used in Example 1.
  • the atmosphere in the airtight container was changed to a nitrogen atmosphere by a vacuum substitution. Then, the pressure was increased to 3.0 MPa at room temperature.
  • the temperature was increased up to 550 °C at a rate of 2 °C/minute while keeping the pressure of 3 MPa, and the pitch molded material was maintained for 1 hour in this state, to form a carbon foam.
  • the carbon foam had a bulk density of 0.50 g/cm 3 . Table 4 shows the results.
  • the carbon foam was temperature-increased under a nitrogen atmosphere at a rate of 10 °C/hour. After the temperature reached to 1,000 °C, the temperature was maintained for 2 hours to calcinate the carbon foam. Successively, the carbon foam was temperature-increased under an argon atmosphere at a rate of 500 °C/hour. At 2,800 °C, a graphitization treatment was carried out for 1 hour, to form a graphite foam.
  • the graphite foam had a bulk density of 0.62 g/cm 3 . Table 4 shows the results.
  • the mesophase pitch had a softening point of 220 °C according to a flow tester, a (H/C) of 0.590, a (Daromatic/Daliphatic) of 0.576 and an aromatic carbon index fa value of 0.863.
  • a carbon foam was produced in the same manner as in Example 11.
  • the carbon foam had a bulk density of 0.25 g/cm 3 .
  • the carbon foam was temperature-increased under a nitrogen atmosphere at a rate of 10 °C/hour. After the temperature reached to 1,000 °C, the temperature was maintained for 2 hours to calcinate the carbon foam. Successively, the carbon foam was temperature-increased under an argon atmosphere at a rate of 500 °C/hour. At 2,800 °C, a graphitization treatment was carried out for 1 hour, to form a graphite foam.
  • the graphite foam had a bulk density of 0.35 g/cm 3 . Table 4 shows the results.
  • Naphthalene was polymerized under the same conditions as those in Example 13, then, the pressure was reduced to recover the catalysts, and further, nitrogen was introduced at 350 °C for 2 hours to obtain a mesophase pitch having an anisotropic content of 70 %.
  • the above mesophase pitch was heat-treated at 450 °C for 1 hour to obtain a heat-treated mesophase pitch having a softening point of 234 °C according to a flow tester, a (H/C) of 0.550, a (Daromatic/Daliphatic) of 1.68 and an aromatic carbon index fa value of 0.937.
  • a carbon foam was produced in the same manner as in Example 1.
  • the carbon foam had a bulk density of 0.28 g/cm 3 .
  • the above carbon foam was temperature-increased under a nitrogen atmosphere at a rate of 10 °C/hour. After the temperature reached to 1,000 °C, the temperature was maintained for 2 hours to calcinate the carbon foam. Successively, the carbon foam was temperature-increased under an argon atmosphere at a rate of 500 °C/hour. At 2,800 °C, a graphitization treatment was carried out for 1 hour, to form a graphite foam.
  • the graphite foam had a bulk density of 0.36 g/cm 3 . Table 5 shows the results.
  • the same mesophase pitch as that used in Example 11 was pulverized with a coffee mill and a solvent extraction was carried out with a toluene solvent by means of a Soxhlet extractor.
  • the extraction residue was an extraction mesophase pitch having a softening point of 300 °C or higher according to a flow tester, a (H/C) of 0.621, a (Daromatic/Daliphatic) of 0.596 and an aromatic carbon index fa value of 0.858.
  • the powder of the extraction mesophase pitch was placed in a cylindrical vessel which was made of aluminum and had an internal diameter of 31 mm, a depth of 40 mm and an internal volume of 30.175 cm 3 , the cylindrical vessel was placed in the same airtight container made of SUS as that used in Example 11.
  • the atmosphere in the airtight container was changed to a nitrogen atmosphere by a vacuum substitution.
  • the pressure was increased to 3.0 MPa at room temperature.
  • the temperature was increased up to 550 °C at a rate of 2 °C/minute while keeping the pressure of 3 MPa.
  • the extraction mesophase pitch powder was maintained for 1 hour in this state, to form a carbon foam.
  • the carbon foam had a bulk density of 0.26 g/cm 3 .
  • the above carbon foam was temperature-increased under a nitrogen atmosphere at a rate of 10 °C/hour. After the temperature reached to 1,000 °C, the temperature was maintained for 2 hours to calcinate the carbon foam. Successively, the carbon foam was temperature-increased under an argon atmosphere at a rate of 500 °C/hour. At 2,800 °C, a graphitization treatment was carried out for 1 hour, to prepare a graphite foam.
  • the graphite foam had a bulk density of 0.34 g/cm 3 . Table 5 shows the results.
  • Example 11 Example 12
  • Example 13 Raw material naphthalene naphthalene naphthalene Synthetic temperature (°C) 265 265 245 Catalyst ratio in synthesis (raw material/HF/BF 3 ) 1/0.35/0.15 1/0.35/0.15 1/0.32/0.074 Post treatment (1) 350°C-10hours nitrogen 350°C-10hours nitrogen 350°C-20hours nitrogen Post treatment (2) 470°C-0.5hour 475°C-0.5hour Nil Extraction with toluene Nil Nil Nil Softening point (°C) 295°C 300°C or higher 220°C H/C 0.526 0.492 0.590 Daroma/Dalipha 1.341 1.806 0.576 fa 0.929 0.947 0.863 Carbon foam Pressure (MPa) 3.0 3.0 3.0 Bulk density d (g/cm 3 ) 0.36 0.50 0.25 Graphite foam Bulk density d (g/cm3) 0.47 0.62 0.35 Darom

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EP02250459A 2001-01-23 2002-01-23 Mousse de carbone, mousse de graphite et leurs procédés de fabrication Withdrawn EP1225160A3 (fr)

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EP1724861A1 (fr) * 2005-05-17 2006-11-22 Nicholas M. Abson Nouveaux matériaux pour les électrolyseurs alcalins et les piles à combustible alcalines
US8399134B2 (en) 2007-11-20 2013-03-19 Firefly Energy, Inc. Lead acid battery including a two-layer carbon foam current collector

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JP2005142439A (ja) * 2003-11-07 2005-06-02 Honda Motor Co Ltd 電気二重層キャパシタ電極用活性炭の製造方法およびその炭素原料
CA2559617A1 (fr) * 2004-03-11 2005-09-22 Benmaxx, Llc Tambour de frein leger renforce et procede de realisation
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US7589041B2 (en) 2004-04-23 2009-09-15 Massachusetts Institute Of Technology Mesostructured zeolitic materials, and methods of making and using the same
US7939046B2 (en) * 2004-06-21 2011-05-10 Raytheon Company Microporous graphite foam and process for producing same
US8226816B2 (en) * 2006-05-24 2012-07-24 West Virginia University Method of producing synthetic pitch
US20080230935A1 (en) * 2006-08-01 2008-09-25 Kennel Elliot B Methods for producing a pitch foam
US20080072476A1 (en) * 2006-08-31 2008-03-27 Kennel Elliot B Process for producing coal liquids and use of coal liquids in liquid fuels
US8449632B2 (en) 2007-05-24 2013-05-28 West Virginia University Sewage material in coal liquefaction
US8465561B2 (en) 2007-05-24 2013-06-18 West Virginia University Hydrogenated vegetable oil in coal liquefaction
US8597503B2 (en) 2007-05-24 2013-12-03 West Virginia University Coal liquefaction system
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US8524625B2 (en) 2009-01-19 2013-09-03 Rive Technology, Inc. Compositions and methods for improving the hydrothermal stability of mesostructured zeolites by rare earth ion exchange
CA2749956C (fr) 2009-01-19 2017-10-31 Rive Technology, Inc. Introduction de mesoporosite dans des zeolites de rapport si/al faible
US8685875B2 (en) 2009-10-20 2014-04-01 Rive Technology, Inc. Methods for enhancing the mesoporosity of zeolite-containing materials
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EP2802534A4 (fr) 2012-01-13 2015-11-18 Rive Technology Inc Introduction de mésoporosité dans des zéolites pauvres en silice
US9376324B2 (en) 2012-01-13 2016-06-28 Rive Technology, Inc. Introduction of mesoporosity into zeolite materials with sequential acid, surfactant, and base treatment
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EP3230208B1 (fr) 2014-12-11 2022-05-18 W. R. Grace & Co.-Conn. Préparation de zéolites mésoporeuses avec traitement réduit
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EP1724861A1 (fr) * 2005-05-17 2006-11-22 Nicholas M. Abson Nouveaux matériaux pour les électrolyseurs alcalins et les piles à combustible alcalines
US8399134B2 (en) 2007-11-20 2013-03-19 Firefly Energy, Inc. Lead acid battery including a two-layer carbon foam current collector

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